U.S. patent application number 10/592563 was filed with the patent office on 2008-11-13 for process for polymerizaing 1-hexene or higher alpha-olefins.
This patent application is currently assigned to Basell Polyotefine GmbH. Invention is credited to Eleonora Ciaccia, Friederike Morhard, Giampaolo Pellegatti, Luigi Resconi.
Application Number | 20080281060 10/592563 |
Document ID | / |
Family ID | 56290670 |
Filed Date | 2008-11-13 |
United States Patent
Application |
20080281060 |
Kind Code |
A1 |
Resconi; Luigi ; et
al. |
November 13, 2008 |
Process For Polymerizaing 1-Hexene or Higher Alpha-Olefins
Abstract
A process for preparing a polymer containing derived units of
one or more alpha olefins of formula CH.sub.2.dbd.CHW wherein W is
a C.sub.3-C.sub.10 hydrocarbon radical and optionally from 0 to 81%
by mol of derived units of propylene or 1-butene, comprising
contacting under polymerization conditions one or more alpha
olefins of formula CH.sub.2.dbd.CHW and optionally propylene or
1-butene in the presence of a catalyst system obtainable by
contacting: a) a metallocene compound of formula (I) ##STR00001##
wherein M, X, L, T.sup.1, T.sup.2, T.sup.3 and R.sup.1 are
described in the text; and (b) an alumoxane or a compound capable
of forming an alkyl metallocene cation.
Inventors: |
Resconi; Luigi; (Ferrara,
IT) ; Ciaccia; Eleonora; (Ferrara, IT) ;
Morhard; Friederike; (Ferrara, IT) ; Pellegatti;
Giampaolo; (Ferrara, IT) |
Correspondence
Address: |
Basell USA Inc.
Delaware Corporate Center II, 2 Righter Parkway, Suite #300
Wilmington
DE
19803
US
|
Assignee: |
Basell Polyotefine GmbH
Wesseling
DE
|
Family ID: |
56290670 |
Appl. No.: |
10/592563 |
Filed: |
March 8, 2005 |
PCT Filed: |
March 8, 2005 |
PCT NO: |
PCT/EP2005/002481 |
371 Date: |
July 18, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60554110 |
Mar 17, 2004 |
|
|
|
60610064 |
Sep 15, 2004 |
|
|
|
Current U.S.
Class: |
526/154 ;
526/170; 526/348.6 |
Current CPC
Class: |
C08F 210/14 20130101;
C08F 210/14 20130101; Y10S 526/943 20130101; C08F 210/06 20130101;
C08F 2500/03 20130101; C08F 2500/03 20130101; C08F 210/08 20130101;
C08F 2500/17 20130101; C08F 2500/17 20130101; C08F 4/65912
20130101; C08F 4/65927 20130101; C08F 210/14 20130101; C08F 210/14
20130101 |
Class at
Publication: |
526/154 ;
526/170; 526/348.6 |
International
Class: |
C08F 4/12 20060101
C08F004/12; C08F 4/72 20060101 C08F004/72; C08F 210/08 20060101
C08F210/08 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 12, 2004 |
EP |
04101020.8 |
Sep 9, 2004 |
EP |
04104351.4 |
Claims
1. A process for preparing a polymer containing derived units of
the at least one alpha olefin of formula CH.sub.2.dbd.CHW wherein W
is a C.sub.3-C.sub.10 hydrocarbon radical and optionally from 0 to
81% by mol of derived units of propylene or 1-butene, comprising
contacting under polymerization conditions at least one alpha
olefin of formula CH.sub.2.dbd.CHW and optionally propylene or
1-butene in the presence of a catalyst system obtained by
contacting: a) a metallocene compound of formula (I): ##STR00011##
wherein: M is an atom of a transition metal selected from those
belonging to group 3, 4, or to the lanthanide or actinide groups in
the Periodic Table of the Elements; X, same or different, is a
hydrogen atom, a halogen atom, or a R, OR, OSO.sub.2CF.sub.3, OCOR,
SR, NR.sub.2 or PR.sub.2 group, wherein R is a are linear or
branched, cyclic or acyclic, C.sub.1-C.sub.40-alkyl,
C.sub.2-C.sub.40 alkenyl, C.sub.2-C.sub.40 alkynyl,
C.sub.6-C.sub.40-aryl, C.sub.7-C.sub.40-alkylaryl or
C.sub.7-C.sub.40-arylalkyl radicals; optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or two X can optionally form a substituted or
unsubstituted butadienyl radical or a OR'O group wherein R' is a
divalent radical selected from C.sub.1-C.sub.40 alkylidene,
C.sub.6-C.sub.40 arylidene, C.sub.7-C.sub.40 alkylarylidene and
C.sub.7-C.sub.40 arylalkylidene radicals; L is a divalent
C.sub.1-C.sub.40 hydrocarbon radical optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements or a divalent silylene radical containing up to 5 silicon
atom; R.sup.1, is a hydrogen atom, or a C.sub.1-C.sub.40
hydrocarbon radicals optionally containing heteroatoms belonging to
groups 13-17 of the Periodic Table of the Elements; T.sup.1 is a
moiety of formula (IIa) or (IIb): ##STR00012## wherein the atom
marked with the symbol * bonds the atom marked with the same symbol
in the compound of formula (I); R.sup.2, R.sup.3 R.sup.4 and
R.sup.5, equal to or different from each other, are hydrogen atoms,
or C.sub.1-C.sub.40 hydrocarbon radicals optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or two adjacent R.sup.2, R.sup.3, R.sup.4 and R.sup.5 can
optionally form a saturated or unsaturated, 5 or 6 membered rings,
said ring can bear C.sub.1-C.sub.20 alkyl radicals as substituents;
R.sup.6 and R.sup.7, equal to or different from each other, are
hydrogen atoms or C.sub.1-C.sub.40 hydrocarbon radicals optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; or R.sup.6 and R.sup.7 can optionally form a
saturated or unsaturated, 5 or 6 membered rings, said ring can bear
C.sub.1-C.sub.20 alkyl radicals as substituents; T.sup.2, equal to
or different from each other, are moieties of formula (IIc) or
(IId): ##STR00013## wherein the atom marked with the symbol * bonds
the atom marked with the same symbol in the compound of formula
(I); R.sup.13, equal to or different from each other, are hydrogen
atoms or C.sub.1-C.sub.40 hydrocarbon radicals optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; R.sup.14, equal to or different from each
other, are hydrogen atoms or C.sub.1-C.sub.40 hydrocarbon radicals
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; and (b) an alumoxane or a compound
that forms an alkyl metallocene cation.
2. The process according to claim 1 wherein the catalyst system
further comprises c) an organo aluminum compound.
3. The process according to claim 1 wherein in the compound of
formula (I), M is titanium, zirconium or hafnium; X is a hydrogen
atom, a halogen atom or a R group, wherein R has been defined as in
claim 1; and L is a divalent bridging group selected from
C.sub.1-C.sub.40 alkylidene, C.sub.3-C.sub.40 cycloalkylidene,
C.sub.6-C.sub.40 arylidene, C.sub.7-C.sub.40 alkylarylidene, or
C.sub.7-C.sub.40 arylalkylidene radicals optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements, and silylene radical containing up to 5 silicon
atoms.
4. The process according to claim 1 wherein in the compound of
formula (I). L is a group (Z(R'').sub.2).sub.n wherein Z is a
carbon or a silicon atom, n is 1 or 2 and R'' is a C.sub.1-C.sub.20
hydrocarbon radical optionally containing heteroatoms belonging to
groups 13-17 of the Periodic Table of the Elements.
5. The process according to claim 1 wherein in the compound of
formula (I), R.sup.1 is linear or branched, saturated or
unsaturated C.sub.1-C.sub.20-alkyl radicals, optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; R.sup.2 is a linear or branched, saturated or unsaturated
C.sub.1-C.sub.20-alkyl radical, optionally containing heteroatoms
belonging to groups 13-17 of the Periodic Table of the Elements;
R.sup.4 is a hydrogen atom or a C.sub.1-C.sub.10-alkyl radical;
R.sup.5 is preferably a hydrogen atom or linear or branched,
saturated or unsaturated C.sub.1-C.sub.20-alkyl radical, optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; R.sup.7 is a hydrogen atom or a linear or
branched, cyclic or acyclic C.sub.1-C.sub.20-alkyl radical; R.sup.6
is a group of formula (III): ##STR00014## wherein R.sup.8, R.sup.9,
R.sup.10, R.sup.11 and R.sup.12, equal to or different from each
other, are hydrogen atoms or C.sub.1-C.sub.20 hydrocarbon
radicals.
6. The process according to claim 1 wherein formula (I) has formula
(IV): ##STR00015## .
7. The process according to claim 1 wherein formula (I) has formula
(V): ##STR00016## .
8. The process according to claim 1 wherein the polymerization
process is carried out using 1-hexene as a polymerization
medium.
9. The process according to claim 1 wherein 1-hexene is
polymerizated.
10. The process according to claim 1 wherein 1-hexene is
copolymerizated with propylene or 1-butene.
11. A copolymer comprising from 41% by mol to 99.9% by mol of
derived units of alpha olefins of formula CH.sub.2.dbd.CHW wherein
W is a C.sub.3-C.sub.10 hydrocarbon radical and from 0.1 to 59% by
mol of derived units of propylene or 1-butene having the following
properties: i) an intrinsic viscosity IV measured
tetrahydronaphtalene (THN) at 135.degree. C. higher than 0.90 dl/g;
ii) a distribution of molecular weight Mw/Mn lower than 3; and iii)
no enthalpy of fusion detectable at a differential scanning
calorimeter (DSC), wherein the DSC measurement is carried out as
described below.
12. The copolymer according to claim 11 further comprising a shore
A lower than 30 and a tensile modulus lower than 20 MPa.
13. A blend comprising a copolymer and a second polymer, the
copolymer obtained by copolymerizing 1-hexene with propylene or
1-butene in the presence of a catalyst system obtained by
contacting: a) a metallocene compound of formula (I): ##STR00017##
wherein: M is an atom of a transition metal selected from those
belonging to group 3, 4, or to the lanthanide or actinide groups in
the Periodic Table of the Elements; X, same or different, is a
hydrogen atom, a halogen atom, or a R, OR, OSO.sub.2CF.sub.3, OCOR,
SR, NR.sub.2 or PR.sub.2 group, wherein R is a are linear or
branched, cyclic or acyclic, C.sub.1-C.sub.40-alkyl,
C.sub.2-C.sub.40 alkenyl, C.sub.2-C.sub.40 alkynyl,
C.sub.6-C.sub.40-aryl, C.sub.7-C.sub.40-alkylaryl or
C.sub.7-C.sub.40-arylalkyl radicals; optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or two X can optionally form a substituted or
unsubstituted butadienyl radical or a OR'O group wherein R' is a
divalent radical selected from C.sub.1-C.sub.40 alkylidene,
C.sub.6-C.sub.40 arylidene, C.sub.7-C.sub.40 alkylarylidene and
C.sub.7-C.sub.40 arylalkylidene radicals; L is a divalent
C.sub.1-C.sub.40 hydrocarbon radical optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements or a divalent silylene radical containing up to 5 silicon
atom: R.sup.1, is a hydrogen atom, or a C.sub.1-C.sub.40
hydrocarbon radicals optionally containing heteroatoms belonging to
groups 13-17 of the Periodic Table of the Elements: T.sup.1 is a
moiety of formula (IIa) or (IIb): ##STR00018## wherein the atom
marked with the symbol * bonds the atom marked with the same symbol
in the compound of formula (I); R.sup.2, R.sup.3 R.sup.4 and
R.sup.5, equal to or different from each other, are hydrogen atoms,
or C.sub.1-C.sub.40 hydrocarbon radicals optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or two adjacent R.sup.2, R.sup.3, R.sup.4 and R.sup.5 can
optionally form a saturated or unsaturated, 5 or 6 membered rings,
said ring can bear C.sub.1-C.sub.10 alkyl radicals as substituents;
R.sup.6 and R.sup.7, equal to or different from each other, are
hydrogen atoms or C.sub.1-C.sub.40 hydrocarbon radicals optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; or R.sup.6 and R.sup.7 can optionally form a
saturated or unsaturated 5 or 6 membered rings, said ring can bear
C.sub.1-C.sub.20 alkyl radicals as substituents; T.sup.2, equal to
or different from each other, are moieties of formula (IIc) or
(IId): ##STR00019## wherein the atom marked with the symbol * bonds
the atom marked with the same symbol in the compound of formula
(I); R.sup.13, equal to or different from each other, are hydrogen
atoms or C.sub.1-C.sub.40 hydrocarbon radicals optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; R.sup.14, equal to or different from each
other, are hydrogen atoms or C.sub.1-C.sub.40 hydrocarbon radicals
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; and (b) an alumoxane or a compound
that forms an alkyl metallocene cation.
14. A process comprising contacting a crystalline matrix, a rubber
phase and a copolymer obtained by copolymerizing 1-hexene with
propylene or 1-butene in the presence of a catalyst system obtained
by contacting: a) a metallocene compound of formula (I):
##STR00020## wherein: M is an atom of a transition metal selected
from those belonging to group 3, 4, or to the lanthanide or
actinide groups in the Periodic Table of the Elements; X, same or
different, is a hydrogen atom, a halogen atom, or a R, OR,
OSO.sub.2CF.sub.3, OCOR, SR, NR.sub.2 or PR.sub.2 group, wherein R
is a are linear or branched, cyclic or acyclic, C.sub.1-C.sub.40
alkyl C.sub.2-C.sub.40 alkenyl, C.sub.2-C.sub.40 alkynyl
C.sub.6-C.sub.40-aryl, C.sub.7-C.sub.40-alkylaryl or
C.sub.7-C.sub.40-arylalkyl radicals; optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or two X can optionally form a substituted or
unsubstituted butadienyl radical or a OR'O group wherein R' is a
divalent radical selected from C.sub.1-C.sub.40 alkylidene
C.sub.6-C.sub.40 arylidene, C.sub.7-C.sub.40 alkylarylidene and
C.sub.7-C.sub.40 arylalkylidene radicals, L is a divalent
C.sub.1-C.sub.40 hydrocarbon radical optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements or a divalent silylene radical containing up to 5 silicon
atom; R.sup.1, is a hydrogen atom, or a C.sub.1-C.sub.40
hydrocarbon radicals optionally containing heteroatoms belonging to
groups 13-17 of the Periodic Table of the Elements; T.sup.1 is a
moiety of formula (IIa) or (IIb): ##STR00021## wherein the atom
marked with the symbol * bonds the atom marked with the same symbol
in the compound of formula (I), R.sup.2, R.sup.3 R.sup.4 and
R.sup.5, equal to or different from each other, are hydrogen atoms,
or C.sub.1-C.sub.40 hydrocarbon radicals optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements, or two adjacent R.sup.2, R.sup.3, R.sup.4 and R.sup.5 can
optionally form a saturated or unsaturated, 5 or 6 membered rings,
said ring can bear C.sub.1-C.sub.20 alkyl radicals as substituents;
R.sup.6 and R.sup.7, equal to or different from each other, are
hydrogen atoms or C.sub.1-C.sub.40 hydrocarbon radicals optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; or R.sup.6 and R.sup.7 can optionally form a
saturated or unsaturated, 5 or 6 membered rings, said ring can bear
C.sub.1-C.sub.20 alkyl radicals as substituents; T.sup.2, equal to
or different from each other are moieties of formula (IIc) or
(IId): ##STR00022## wherein the atom marked with the symbol * bonds
the atom marked with the same symbol in the compound of formula
(I): R.sup.13, equal to or different from each other, are hydrogen
atoms or C.sub.1-C.sub.40 hydrocarbon radicals optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; R.sup.14, equal to or different from each
other, are hydrogen atoms or C.sub.1-C.sub.40 hydrocarbon radicals
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; and (b) an alumoxane or a compound
that forms an alkyl metallocene cation wherein the copolymer is a
compatibilzer between the crystalline matrix and the rubber phase.
Description
[0001] This application is the U.S. national phase of International
Application PCT/EP2005/002481, filed Mar. 8, 2005, claiming
priority to European Patent Application 04101020.8 filed Mar. 12,
2004, and European Patent Application 04104351.4 filed Sep. 9,
2004, and the benefit under 35 U.S.C. 119(e) of U.S. Provisional
Application No. 60/554,110, filed Mar. 17, 2004 and U.S.
Provisional Application No. 60/610,064 filed Sep. 15, 2004; the
disclosures of International Application PCT/EP2005/002481,
European Patent Applications 04101020.8 and 04104351.4 and U.S.
Provisional Application Nos. 60/554,110 and 60/610,064, each as
filed, are incorporated herein by reference.
[0002] The present invention relates to a process for obtaining a
polymer comprising 1-hexene or higher alpha-olefins derived units,
by using a specific class of metallocene compounds, that allows to
obtain polymers having high molecular weight in high yields.
Metallocene compounds are well known catalyst components for the
polymerization of alpha-olefins. However they are mainly used for
the (co)polymerization of ethylene, propylene and 1-butene.
Polymerization of 1-hexene and higher alpha olefins by using
metallocene catalyst components is discussed in some papers. For
example U.S. Pat. No. 6,566,544 discloses in table 10 the
polymerization of 1-hexene by using Ind.sub.2ZrMe.sub.2 and
bis(2-phenylindenyl)zirconium dimethyl. The molecular weight of the
obtained polymers are quite low. In Macromol. Chem. Phys. 200,
1208-1219 (1999), 1-hexene is polymerized in the presence of
iPr(CpFlu)ZrCl.sub.2. The polymer has a syndiotactic structure and
the molecular mass of the polymer obtained is close to 20000
gmol.sup.-1. In Journal of Polymer Science: Part A: Polymer
Chemistry, Vol 37, 283-292 (1999) a series of metallocene compounds
have been tested in 1-hexene polymerization.
Rac-[Me.sub.2Ge(.eta..sup.5-C.sub.5H-2,3,5-Me.sub.3)MCl.sub.2 (M=Zr
or Hf) allows to obtain 1-hexene polymers having a very high
molecular weight. However the drawback of this compound is that it
is necessary to separate the racemic from the meso form, this makes
the synthesis of such compound much more difficult and expensive
than the metallocene compound of the present invention. In the same
article is also shown that
isopropyliden(9-fluorenyl)(cyclopentadienyl)zirconium dichloride
produces 1-hexene polymer having very low molecular weight, with
respect to the other compounds tested. The behaviour of
isopropyliden(9-fluorenyl)(cyclopentadienyl)zirconium dichloride is
confirmed in Macromol. Mater. Eng. 2001, 286, 480-487. In this
paper the molecular weight (Mw) of 1-hexene polymer obtained by
using said compound is about 45000.
[0003] WO 01/46278 relates to a polymerization process for
producing a copolymer containing from 60 to 94% mol of alpha
olefins having from 3 to 6 carbon atoms, and from 6 to 40% mol of
alpha olefins having at least one carbon atom more than the first
one. In the examples propylene is copolymerized with 1-hexene.
These copolymers are obtained with a metallocene compound different
from that one used in the present invention, moreover the molecular
weight of the obtained copolymers can still be improved. Finally
the present invention is directed to a copolymer that contains a
smaller amount of propylene or 1-butene.
[0004] In Macromol. Chem. Phys. 197, 563-573 (1996) are described a
series of hexene propylene copolymers having various content of
comonomer from 0 to 100% by mol. The copolymers are obtained by
using Et(Ind).sub.2HfCl.sub.2 and both the yields and the molecular
weight of the obtained polymers can be further improved.
[0005] Thus there is still the need to find a class of metallocene
compounds easy to prepare and without the drawback to separate the
racemic from the meso form able to give 1-hexene or higher
alpha-olefins (co)polymers having an high molecular weight in high
yields. An object of the present invention is a process for
preparing a polymer containing derived units of one or more alpha
olefins of formula CH.sub.2.dbd.CHW wherein W is a C.sub.3-C.sub.10
hydrocarbon radical and optionally from 0 to 81% by mol; preferably
from 0 to 70% by mol, more preferably from 0 to 59% by mol, of
derived units of propylene or 1-butene, comprising contacting under
polymerization conditions one or more alpha olefins of formula
CH.sub.2.dbd.CHW and optionally propylene or 1-butene in the
presence of a catalyst system obtainable by contacting: [0006] a) a
metallocene compound of formula (I)
[0006] ##STR00002## [0007] wherein: [0008] M is an atom of a
transition metal selected from those belonging to group 3, 4, or to
the lanthanide or actinide groups in the Periodic Table of the
Elements; preferably M is zirconium titanium or hafnium; [0009] X,
same or different, is a hydrogen atom, a halogen atom, or a R, OR,
OSO.sub.2CF.sub.3, OCOR, SR, NR.sub.2 or PR.sub.2 group, wherein R
is a are linear or branched, cyclic or acyclic,
C.sub.1-C.sub.40-alkyl, C.sub.2-C.sub.40 alkenyl, C.sub.2-C.sub.40
alkynyl, C.sub.6-C.sub.40-aryl, C.sub.7-C.sub.40-alkylaryl or
C.sub.7-C.sub.40-arylalkyl radicals; optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or two X can optionally form a substituted or
unsubstituted butadienyl radical or a OR'O group wherein R' is a
divalent radical selected from C.sub.1-C.sub.40 alkylidene,
C.sub.6-C.sub.40 arylidene, C.sub.7-C.sub.40 alkylarylidene and
C.sub.7-C.sub.40 arylalkylidene radicals; preferably X is a
hydrogen atom, a halogen atom or a R group; more preferably X is
chlorine or a C.sub.1-C.sub.10-alkyl radical; such as methyl, or
ethyl radicals; [0010] L is a divalent C.sub.1-C.sub.40 hydrocarbon
radical optionally containing heteroatoms belonging to groups 13-17
of the Periodic Table of the Elements or a divalent silylene
radical containing up to 5 silicon atom; preferably L is a divalent
bridging group selected from C.sub.1-C.sub.40 alkylidene,
C.sub.3-C.sub.40 cycloalkylidene, C.sub.6-C.sub.40 arylidene,
C.sub.7-C.sub.40 alkylarylidene, or C.sub.7-C.sub.40 arylalkylidene
radicals optionally containing heteroatoms belonging to groups
13-17 of the Periodic Table of the Elements, and silylene radical
containing up to 5 silicon atoms such as SiMe.sub.2, SiPh.sub.2;
preferably L is a group (Z(R'').sub.2).sub.r wherein Z is a carbon
or a silicon atom, n is 1 or 2 and R'' is a C.sub.1-C.sub.20
hydrocarbon radical optionally containing heteroatoms belonging to
groups 13-17 of the Periodic Table of the Elements; preferably R''
is a linear or branched, cyclic or acyclic, C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl,
C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-alkylaryl or
C.sub.7-C.sub.20-arylalkyl radicals optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; more preferably the group (Z(R'').sub.2).sub.n is
Si(CH.sub.3).sub.2, SiPh.sub.2, SiPhMe, SiMe(SiMe.sub.3), CH.sub.2,
(CH.sub.2).sub.2, and C(CH.sub.3).sub.2; [0011] R.sup.1, is a
hydrogen atom, or a C.sub.1-C.sub.40 hydrocarbon radicals
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; Preferably R.sup.1 is a hydrogen
atom or a linear or branched, cyclic or acyclic,
C.sub.1-C.sub.40-alkyl, C.sub.2-C.sub.40 alkenyl, C.sub.2-C.sub.40
alkynyl, C.sub.6-C.sub.40-aryl, C.sub.7-C.sub.40-alkylaryl or
C.sub.7-C.sub.40-arylalkyl radicals; optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; more preferably R.sup.1 is linear or branched, saturated
or unsaturated C.sub.1-C.sub.20-alkyl radicals, optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; even more preferably R.sup.1 is a
C.sub.1-C.sub.10-alkyl radical such as a methyl, or ethyl radical;
[0012] T.sup.1 is a moiety of formula (IIa) or (IIb):
[0012] ##STR00003## [0013] wherein the atom marked with the symbol
* bonds the atom marked with the same symbol in the compound of
formula (I); [0014] R.sup.2, R.sup.3, R.sup.4 and R.sup.5, equal to
or different from each other, are hydrogen atoms, or
C.sub.1-C.sub.40 hydrocarbon radicals optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or two adjacent R.sup.2, R.sup.3, R.sup.4 and R.sup.5 can
optionally form a saturated or unsaturated, 5 or 6 membered rings,
said ring can bear C.sub.1-C.sub.20 alkyl radicals as substituents;
Preferably R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are hydrogen atoms
or linear or branched, cyclic or acyclic, C.sub.1-C.sub.40-alkyl,
C.sub.2-C.sub.40 alkenyl, C.sub.2-C.sub.40 alkynyl,
C.sub.6-C.sub.40-aryl, C.sub.7-C.sub.40-alkylaryl or
C.sub.7-C.sub.40-arylalkyl radicals; optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; [0015] R.sup.2 is preferably a linear or branched,
saturated or unsaturated C.sub.1-C.sub.20-alkyl radical, optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; preferably R.sup.2 is a
C.sub.1-C.sub.10-alkyl radical; more preferably R.sup.2 is a
methyl, ethyl or isopropyl radical; [0016] R.sup.4 is preferably a
hydrogen atom or a C.sub.1-C.sub.10-alkyl radical such as a methyl,
ethyl or isopropyl radical; [0017] R.sup.5 is preferably a hydrogen
atom or linear or branched, saturated or unsaturated
C.sub.1-C.sub.20-alkyl radical, optionally containing heteroatoms
belonging to groups 13-17 of the Periodic Table of the Elements;
preferably a C.sub.1-C.sub.10-alkyl radical; more preferably
R.sup.5 is a methyl or ethyl radical; [0018] R.sup.6 and R.sup.7,
equal to or different from each other, are hydrogen atoms or
C.sub.1-C.sub.40 hydrocarbon radicals optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or R.sup.6 and R.sup.7 can optionally form a saturated or
unsaturated, 5 or 6 membered rings, said ring can bear
C.sub.1-C.sub.20 alkyl radicals as substituents; preferably R.sup.6
and R.sup.7 are hydrogen atoms or linear or branched, cyclic or
acyclic, C.sub.1-C.sub.40-alkyl, C.sub.2-C.sub.40 alkenyl,
C.sub.2-C.sub.40 alkynyl, C.sub.6-C.sub.40-aryl,
C.sub.7-C.sub.40-alkylaryl or C.sub.7-C.sub.40-arylalkyl radicals;
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; [0019] preferably R.sup.7 is a
hydrogen atom or a linear or branched, cyclic or acyclic
C.sub.1-C.sub.20-alkyl radical; more preferably R.sup.7 is a methyl
or ethyl radical; preferably R.sup.6 is a C.sub.1-C.sub.40-alkyl,
C.sub.6-C.sub.40-aryl or a C.sub.7-C.sub.40-arylalkyl; more
preferably R.sup.6 is a group of formula (III)
[0019] ##STR00004## [0020] wherein R.sup.8, R.sup.9, R.sup.10,
R.sup.11 and R.sup.12, equal to or different from each other, are
hydrogen atoms or C.sub.1-C.sub.20 hydrocarbon radicals; preferably
R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are hydrogen
atoms or linear or branched, cyclic or acyclic,
C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20
alkynyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-alkylaryl or
C.sub.7-C.sub.20-arylalkyl radicals; preferably R.sup.8, and
R.sup.11 are a hydrogen atoms; R.sup.9, R.sup.10 and R.sup.12 are
preferably hydrogen atoms or linear or branched, cyclic or acyclic,
C.sub.1-C.sub.10-alkyl radicals; [0021] T.sup.2, equal to or
different from each other, are moieties of formula (IIc) or
(IId):
[0021] ##STR00005## [0022] wherein the atom marked with the symbol
* bonds the atom marked with the same symbol in the compound of
formula (I); [0023] R.sup.13, equal to or different from each
other, are hydrogen atoms or C.sub.1-C.sub.40 hydrocarbon radicals
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; or two R.sup.13 can optionally form
a saturated or unsaturated, 5 or 6 membered rings, said ring can
bear C.sub.1-C.sub.20 alkyl radicals as substituents; preferably
R.sup.13 are hydrogen atoms or linear or branched, cyclic or
acyclic, C.sub.1-C.sub.40-alkyl, C.sub.2-C.sub.40 alkenyl,
C.sub.2-C.sub.40 alkynyl, C.sub.6-C.sub.40-aryl,
C.sub.7-C.sub.40-alkylaryl or C.sub.7-C.sub.40-arylalkyl radicals;
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; more preferably R.sup.13 are a
hydrogen atoms or linear or branched, C.sub.1-C.sub.20-alkyl
radicals; [0024] R.sup.14, equal to or different from each other,
are hydrogen atoms or C.sub.1-C.sub.40 hydrocarbon radicals
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; preferably R.sup.14 are linear or
branched, cyclic or acyclic, C.sub.1-C.sub.40-alkyl,
C.sub.2-C.sub.40 alkenyl, C.sub.2-C.sub.40 alkynyl,
C.sub.6-C.sub.40-aryl, C.sub.7-C.sub.40-alkylaryl or
C.sub.7-C.sub.40-arylalkyl radicals; optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; more preferably R.sup.14 are linear or branched,
C.sub.1-C.sub.20-alkyl radicals; [0025] (b) an alumoxane or a
compound capable of forming an alkyl metallocene cation; and
optionally [0026] (c) an organo aluminum compound.
[0027] In one embodiment the compound of formula (I) has the
following formula (IV)
##STR00006##
wherein M, X, L, R.sup.1, R.sup.6, R.sup.7, and R.sup.14 are
described above.
[0028] In a further alternative embodiment the compound of formula
(I) has the following formula (V)
##STR00007##
wherein M, X, L, R.sup.1, R.sup.2, R.sup.5 and R.sup.14 are
described above. compounds of formula (I) are well know in the art,
they can be prepared for example as described in WO 01/47939 or EP
707 016.
[0029] Alumoxanes used as component b) can be obtained by reacting
water with an organo-aluminium compound of formula
H.sub.jAlU.sub.3-j or H.sub.jAl.sub.2U.sub.6-j, where the U
substituents, same or different, are hydrogen atoms, halogen atoms,
C.sub.1-C.sub.20-alkyl, C.sub.3-C.sub.20-cyclalkyl,
C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-alkylaryl or
C.sub.7-C.sub.20-arylalkyl radicals, optionally containing silicon
or germanium atoms, with the proviso that at least one U is
different from halogen, and j ranges from 0 to 1, being also a
non-integer number. In this reaction the molar ratio of Al/water is
preferably comprised between 1:1 and 100:1.
[0030] Alumoxanes used as component b) can be obtained by reacting
water with an organo-aluminium compound of formula
H.sub.jAlU.sub.3-j or H.sub.jAl.sub.2U.sub.6-j, where the U
substituents, same or different, are hydrogen atoms, halogen atoms,
C.sub.1-C.sub.20-allyl, C.sub.3-C.sub.20-cyclalkyl,
C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-alkylaryl or
C.sub.7-C.sub.20-arylalkyl radicals, optionally containing silicon
or germanium atoms, with the proviso that at least one U is
different from halogen, and j ranges from 0 to 1, being also a
non-integer number. In this reaction the molar ratio of Al/water is
preferably comprised between 1:1 and 100:1.
[0031] The alumoxanes used in the process according to the
invention are considered to be linear, branched or cyclic compounds
containing at least one group of the type:
##STR00008##
wherein the substituents U, same or different, are defined
above.
[0032] In particular, alumoxanes of the formula:
##STR00009##
can be used in the case of linear compounds, wherein n.sup.1 is 0
or an integer of from 1 to 40 and the substituents U are defined as
above; or alumoxanes of the formula:
##STR00010##
can be used in the case of cyclic compounds, wherein n.sup.2 is an
integer from 2 to 40 and the U substituents are defined as
above.
[0033] Examples of alumoxanes suitable for use according to the
present invention are methylalumoxane (MAO),
tetra-(isobutyl)alumoxane (TIBAO),
tetra-(2,4,4-trimethyl-pentyl)alumoxane (TIOAO),
tetra-(2,3-dimethylbutyl)alumoxane (TDMBAO) and
tetra-(2,3,3-trimethylbutyl)alumoxane (TTMBAO).
[0034] Particularly interesting cocatalysts are those described in
WO 99/21899 and in WO01/21674 in which the alkyl and aryl groups
have specific branched patterns.
[0035] Non-limiting examples of aluminium compounds that can be
reacted with water to give suitable alumoxanes (b), described in WO
99/21899 and WO01/21674, are: tris(2,3,3-trimethyl-butyl)aluminium,
tris(2,3-dimethyl-hexyl)aluminium,
tris(2,3-dimethyl-butyl)aluminium,
tris(2,3-dimethyl-pentyl)aluminium,
tris(2,3-dimethyl-heptyl)aluminium,
tris(2-methyl-3-ethyl-pentyl)aluminium,
tris(2-methyl-3-ethyl-hexyl)aluminium,
tris(2-methyl-3-ethyl-heptyl)aluminium,
tris(2-methyl-3-propyl-hexyl)aluminium,
tris(2-ethyl-3-methyl-butyl)aluminium,
tris(2-ethyl-3-methyl-pentyl)aluminium,
tris(2,3-diethyl-pentyl)aluminium,
tris(2-propyl-3-methyl-butyl)aluminium,
tris(2-isopropyl-3-methyl-butyl)aluminium,
tris(2-isobutyl-3-methyl-pentyl)aluminium,
tris(2,3,3-trimethyl-pentyl)aluminium,
tris(2,3,3-trimethyl-hexyl)aluminium,
tris(2-ethyl-3,3-dimethyl-butyl)aluminium,
tris(2-ethyl-3,3-dimethyl-pentyl)aluminium,
tris(2-isopropyl-3,3-dimethyl-butyl)aluminium,
tris(2-trimethylsilyl-propyl)aluminium,
tris(2-methyl-3-phenyl-butyl)aluminium,
tris(2-ethyl-3-phenyl-butyl)aluminium,
tris(2,3-dimethyl-3-phenyl-butyl)aluminium,
tris(2-phenyl-propyl)aluminium,
tris[2-(4-fluoro-phenyl)-propyl]aluminium,
tris[2-(4-chloro-phenyl)-propyl]aluminium,
tris[2-(3-isopropyl-phenyl)-propyl]aluminium,
tris(2-phenyl-butyl)aluminium,
tris(3-methyl-2-phenyl-butyl)aluminium,
tris(2-phenyl-pentyl)aluminium,
tris[2-(pentafluorophenyl)-propyl]aluminium,
tris[2,2-diphenyl-ethyl]aluminium and
tris[2-phenyl-2-methyl-propyl]aluminium, as well as the
corresponding compounds wherein one of the hydrocarbyl groups is
replaced with a hydrogen atom, and those wherein one or two of the
hydrocarbyl groups are replaced with an isobutyl group.
[0036] Amongst the above aluminium compounds, trimethylaluminium
(TMA), triisobutylaluminium (TTBA),
tris(2,4,4-trimethyl-pentyl)aluminium (TIOA),
tris(2,3-dimethylbutyl)aluminium (TDMBA) and
tris(2,3,3-trimethylbutyl)aluminium (TTMBA) are preferred.
[0037] Non-limiting examples of compounds able to form an
alkylmetallocene cation are compounds of formula D.sup.+E.sup.-,
wherein D.sup.+ is a Bronsted acid, able to donate a proton and to
react irreversibly with a substituent X of the metallocene of
formula (I) and E.sup.- is a compatible anion, which is able to
stabilize the active catalytic species originating from the
reaction of the two compounds, and which is sufficiently labile to
be removed by an olefinic monomer. Preferably, the anion E.sup.-
comprises one or more boron atoms. More preferably, the anion
E.sup.- is an anion of the formula BAr.sub.4.sup.(-), wherein the
substituents Ar which can be identical or different are aryl
radicals such as phenyl, pentafluorophenyl or
bis(trifluoromethyl)phenyl. Tetrakis-pentafluorophenyl borate is
particularly preferred compound, as described in WO 91/02012.
Moreover, compounds of formula BAr.sub.3 can be conveniently used.
Compounds of this type are described, for example, in the
International patent application WO 92/00333. Other examples of
compounds able to form an alkylmetallocene cation are compounds of
formula BAr.sub.3P wherein P is a substituted or unsubstituted
pyrrol radical. These compounds are described in WO01/62764.
Compounds containing boron atoms can be conveniently supported
according to the description of DE-A-19962814 and DE-A-19962910.
All these compounds containing boron atoms can be used in a molar
ratio between boron and the metal of the metallocene comprised
between about 1:1 and about 10:1; preferably 1:1 and 2.1; more
preferably about 1:1.
[0038] Non limiting examples of compounds of formula D.sup.+E.sup.-
are: [0039] Triethylammoniumtetra(phenyl)borate, [0040]
Tributylammoniumtetra(phenyl)borate, [0041]
Trimethylammoniumtetra(tolyl)borate, [0042]
Tributylammoniumtetra(tolyl)borate, [0043]
Tributylammoniumtetra(pentafluorophenyl)borate, [0044]
Tributylammoniumtetra(pentafluorophenyl)aluminate, [0045]
Tripropylammoniumtetra(dimethylphenyl)borate, [0046]
Tributylammoniumtetra(trifluoromethylphenyl)borate, [0047]
Tributylammoniumtetra(4-fluorophenyl)borate, [0048]
N,N-Dimethylbenzylammonium-tetrakispentafluorophenylborate, [0049]
N,N-Dimethylhexylamonium-tetrakispentafluorophenylborate, [0050]
N,N-Dimethylaniliniumtetra(phenyl)borate, [0051]
N,N-Diethylaniliniumtetra(phenyl)borate, [0052]
N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)borate, [0053]
N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)aluminate, [0054]
N,N-Dimethylbenzylammonium-tetrakispentafluorophenylborate, [0055]
N,N-Dimethylhexylamonium-tetrakispentafluorophenylborate, [0056]
Di(propyl)ammoniumtetrakis(pentafluorophenyl)borate, [0057]
Di(cyclohexyl)ammoniumtetrakis(pentafluorophenyl)borate, [0058]
Triphenylphosphoniumtetrakis(phenyl)borate, [0059]
Triethylphosphoniumtetrakis(phenyl)borate, [0060]
Diphenylphosphoniumtetrakis(phenyl)borate, [0061]
Tri(methylphenyl)phosphoniumtetrakis(phenyl)borate, [0062]
Tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate, [0063]
Triphenylcarbeniumtetrakis(pentafluorophenyl)borate, [0064]
Triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate, [0065]
Triphenylcarbeniumtetrakis(phenyl)aluminate, [0066]
Ferroceniumtetrakis(pentafluorophenyl)borate, [0067]
Ferroceniumtetrakis(pentafluorophenyl)aluminate. [0068]
Triphenylcarbeniumtetrakis(pentafluorophenyl)borate, and [0069]
N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)borate.
[0070] Organic aluminum compounds used as compound iii) are those
of formula H.sub.jAlU.sub.3-j or H.sub.jAl.sub.2U.sub.6-j as
described above.
[0071] The polymerization process of the present invention can be
carried out in liquid phase, optionally in the presence of an inert
hydrocarbon solvent. Said hydrocarbon solvent can be either
aromatic (such as toluene) or aliphatic (such as propane, hexane,
heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane).
Preferably, the polymerization process of the present invention is
carried out by using the alpha olefin of formula CH.sub.2.dbd.CHW
wherein W is a C.sub.3-C.sub.10 hydrocarbon radical such as
1-hexene or 1-octene as polymerization medium, i.e. the same olefin
that is going to be polymerizated for example 1-hexene is used as
polymerization medium when a 1-hexene-based polymer is the wished
polymer.
[0072] The polymerization temperature preferably ranges from
0.degree. C. to 250.degree. C.; more preferably it is comprised
between 20.degree. C. and 150.degree. C. and, more particularly the
polymerization temperature is between 40.degree. C. and 90.degree.
C.;
[0073] The molecular weight distribution can be varied by using
mixtures of different metallocene compounds or by carrying out the
polymerization in several stages which differ as to the
polymerization temperature and/or the concentrations of the
molecular weight regulators and/or the monomers concentration.
Moreover by carrying out the polymerization process by using a
combination of two different metallocene compounds of formula (I) a
polymer endowed with a broad melting is produced.
[0074] With the process of the present invention isotactic polymers
endowed with high molecular weights can be obtained in high
yields.
[0075] With the process of the present invention polymers
containing derived units of one or more alpha olefins of formula
CH.sub.2.dbd.CHW wherein W is a C.sub.3-C.sub.10 hydrocarbon
radical and optionally from 0 to 81% by mol of derived units of
propylene or 1-butene can be obtained. Examples of alpha olefins of
formula CH.sub.2.dbd.CHW are 1-pentene; 1-hexene; 1-octene and
1-decene. Preferably 1-hexene and 1-octene are used; more
preferably 1-hexene is used.
[0076] When said alpha olefins of formula CH.sub.2.dbd.CHW are
copolimerized with propylene or 1-butene preferably the obtained
copolymer has a content of derived units of propylene or 1-butene
ranging from 0.1% by mol to 59% by mol; more preferably the content
of propylene or 1-butene ranges from 10% by mol to 50% by mol, even
more preferably it ranges from 19% by mol to 40% by mol.
[0077] The obtained copolymer is endowed with the following
properties: [0078] i) intrinsic viscosity IV measured in
tetrahydronaphtalene (THN) at 135.degree. C. higher than 0.90 dl/g;
preferably higher than 1.20 dl/g; more preferably higher than 1.30
dl/g; even more preferably higher than 1.80 dl/g; [0079] ii)
distribution of molecular weight Mw/Mn lower than 3; preferably
lower than 2.5; and [0080] iii) no enthalpy of fusion detectable at
a differential scanning calorimeter (DSC) wherein the DSC
measurement is carried out as described below.
[0081] Preferably in said copolymers the alpha olefin of formula
CH.sub.2.dbd.CHW is 1-hexene or 1-octene.
[0082] The copolymers, other than the above properties, are further
endowed with a very low Shore A (measured according to ISO 868), in
particular the shore A is lower than 30; preferably lower than 25;
more preferably lower than 20; and furthermore the tensile modulus
is lower than 20 MPa (measured according to ASTM 5026,4092 e 4065);
preferably lower than 15 MPa; more preferably lower than 11
MPa.
[0083] A further preferred range of content of derived units of
propylene and 1-butene is from 19% by mol to 59% by mol; even more
preferably from 30% by mol to 59% by mol.
[0084] The process of the present invention is particularly
suitable for preparing homopolymers of alpha olefins of formula
CH.sub.2.dbd.CHW wherein W is a C.sub.3-C.sub.10 hydrocarbon
radical, in particular homopolymers of 1-hexene or 1-octene;
preferably homopolymer of 1-hexene are produced.
[0085] The homopolymer prepared according to the present invention
can be used for application known in the art such as masterbaches
or in adhesive formulations.
[0086] Even if the homopolymer of the present invention are not
exemplified, their preparation can be easily achieved by the
skilled man once it is know the process for preparing the
copolymers. In fact it is sufficient to avoid to add the comonomer
in the processes exemplified above for obtaining the wished
homopolymer.
[0087] The copolymers obtainable with the process of the present
invention described above, can have the same uses of the
homopolymer and furthermore they can be used as compatibilizer. For
example they can improve the dispersion of a rubber phase in an
crystalline matrix, due to the presence of the comonomer that help
to compatibilize the two phases, so that a material having an
improved izod impact value con be obtained.
[0088] The following examples are given to illustrate and not to
limit the invention.
EXAMPLES
General Procedures and Characterizations
[0089] All chemicals were handled under nitrogen using standard
Schlenk techniques. Methylalumoxane (MAO) was received from
Albemarle as a 30% wt/vol toluene solution and used as such.
[0090] Pure triisobutylaluminum (TIBA) was used as such.
[0091] Isododecane was purified over aluminum oxide to reach a
water content below 10 ppm. A 101 g/L TIBA/isododecane solution was
obtained by mixing the above components.
[0092] The melting points of the polymers (T.sub.m) were measured
by Differential Scanning Calorimetry (D.S.C.) on a Perkin Elmer
DSC-7 instrument, according to the standard method. A weighted
sample (5-7 mg) obtained from the polymerization was sealed into
aluminum pans and heated to 180.degree. C. at 10.degree. C./minute.
The sample was kept at 180.degree. C. for 5 minutes to allow a
complete melting of all the crystallites, then cooled to 20.degree.
C. at 10.degree. C./minute. After standing 2 minutes at 20.degree.
C., the sample was heated for the second time to 180.degree. C. at
10.degree. C./min. In this second heating run, the peak temperature
was taken as the melting temperature (T.sub.m) and the area of the
peak as melting enthalpy (.DELTA.H.sub.f).
[0093] Molecular weight parameters were measured using a Waters
150C ALC/GPC instrument (Waters, Milford, Mass., USA) equipped with
four mixed-gel columns PLgel 20 .mu.m Mixed-A LS (Polymer
Laboratories, Church Stretton, United Kingdom). The dimensions of
the columns were 300.times.7.8 mm. The solvent used was TCB and the
flow rate was kept at 1.0 mL/min. Solution concentrations were 0.1
g/dL in 1,2,4 trichlorobenzene (TCB). 0.1 g/L of
2,6-di-t-butyl-4-methyl phenol (BHT) was added to prevent
degradation and the injection volume was 300 .mu.L. All the
measurements were carried out at 135.degree. C. GPC calibration is
complex, as no well-characterized narrow molecular weight
distribution standard reference materials are available for
1-hexene polymers. Thus, a universal calibration curve was obtained
using 12 polystyrene standard samples with molecular weights
ranging from 580 to 13,200,000. It was assumed that the K values of
the Mark-Houwink relationship were: K.sub.PS=1.21.times.10.sup.-4,
dL/g and K.sub.PH=1.78.times.10.sup.-4 dL/g for polystyrene and
poly-1-hexene respectively, for the copolymers the same K.sub.PH
has been used. The Mark-Houwink exponents a were assumed to be
0.706 for polystyrene and 0.725 for poly-1-hexene and copolymers.
Even though, in this approach, the molecular parameters obtained
were only an estimate of the hydrodynamic volume of each chain,
they allowed a relative comparison to be made.
[0094] The intrinsic viscosity (I.V.) was measured in
tetrahydronaphtalene (THN) at 135.degree. C. Rac
dimethylsilyl{(2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2--
b:4,3-b']-dithiophene)}zirconium dimethyl (A-1) was prepared
according to the following procedure: the ligand,
[3-(2,4,7-trimethylindenyl)][7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dit-
hiophene)]dimethyl silane, was prepared as described in WO
01/47939. 30.40 g of this ligand (72.26 mmol) and 170 ml of
anhydrous THF were charged under nitrogen in a cilindrical glass
reactor equipped with magnetic stirring bar. The brown solution so
obtained was cooled and maintained at 0.degree. C., while 58.4 ml
of n-BuLi 2.5M in hexane (146 mmol) were added dropwise via
dropping funnel. At the end of the addition, the dark brown
solution was stirred for 1 hour at room temperature, then cooled to
-50.degree. C., and then 48.6 ml of MeLi 3.05 M in diethoxymethane
(148.2 mmol) were added to it. In a Schlenk, 16.84 g of ZrCl.sub.4
(72.26 mmol) were slurried in 170 ml of toluene. Both mixtures were
kept at -50.degree. C. and the ZrCl.sub.4 slurry was quickly added
to the ligand dianion solution. At the end of the addition, the
reaction mixture was allowed to reach room temperature and stirred
for an additional hour. A yellow-green suspension was obtained.
.sup.1H NMR analysis shows complete conversion to the target
complex. All volatiles were removed under reduced pressure, and the
obtained free flowing brown powder was suspended in 100 ml of
Et.sub.2O. After stirring for a few minutes, the suspension was
filtered over a G4 frit. The solid on the frit was then washed
twice with Et.sub.2O (until the washing solvent turns from brown to
yellow), then dried under vacuum, and finally extracted on the frit
with warm toluene (60.degree. C.), until the filtering solution
turns from yellow to colorless (about 650 ml of toluene); The
extract was dried under reduced pressure to give 28.6 g of yellow
powder, which .sup.1H-NMR showed to be the target complex, free
from impurities. The yield based on the ligand was 73.3%.
[0095] .sup.1H-NMR: (CD.sub.2Cl.sub.2, r.t.), ppm: -2.09 (s, 3H),
-0.79 (s, 3H), 1.01 (s, 3H), 1.04 (s, 3H), 2.38 (s, 3H), 2.39 (s,
3H), 2.43 (d, 3H, J=1.37 Hz), 2.52 (s, 3H), 2.57 (d, 3H, J=1.37
Hz), 6.61 (dq, 1H, J=7.04 Hz, J=0.78 Hz), 6.81 (q, 1H, J=1.37 Hz),
6.85 (dq, 1H, J=7.04 Hz, J=0.78 Hz), 6.87 (q, 1H, J=1.37 Hz), 6.91
(s, 1H).
[0096] Flexural modulus, stress at break and elongation at break
have been measured according to ISO 527-1 and ISO 178, Stress at
yield and elongation at yield have been measured according to ASTM
D 638, tensile modulus has been measured according to ASTM D 790,
melt flow rate under the condition 230.degree. C./2.16 kg is
measured according to ISO 1133. Izod has been measured according to
ASTM D256.
Preparation of Catalyst Systems
Preparation of Catalyst System C-1
[0097] 9.7 cc of TIBA/isododecane solution were mixed with 1.9 cc
of 30% MAO/toluene solution (MAO/TIBA, molar ratio 2:1). Then, 20
mg of A-1 were dissolved with this solution. The metallocene was
completely soluble, the dark violet solution did not show any trace
of residual solid. The final solution was obtained upon recovery of
2.0 cc by distillation. MAO/TIBA 2:1 mol/mol; Al.sub.tot/Zr=400.
This solution was used to perform 1-hexene polymerization.
Polymerization Tests
[0098] 1-hexene Homopolymerization, General Procedure.
[0099] To 20 g of liquid 1-hexene an amount of the catalyst
solution obtained as reported above containing 0.5 mg of
metallocene, is added at 50.degree. C. After 30 minutes, the
polymerization is stopped with ethanol. Then, acetone is added to
separate the polymer. Finally, the polymer is dried at 50.degree.
C. under vacuum for several hours. The results of the 1-hexene
polymerization tests are reported in Table 1.
TABLE-US-00001 TABLE 1 1-hexene polymerization results. Ex Cat.
Ageing, days Yield, g Activity Kg/g.sub.meth 1 C-1 1 13.46 53.8
Preparation of Catalyst System C-2 A1/MAO:TIBA 2:1 (400)
[0100] 33.3 ml of TIBA/isododecane solution (101 g/L) was mixed
with 7.9 cc of MAO/toluene solution (Albemarle -30% wt) to obtain a
MAO/TIBA molar ratio of 2:1. The solution was stirred for 1 hour at
room temperature. Then, 69 mg of A-1 was dissolved in the
solution.
[0101] The dark violet solution did not show any trace of residual
solid.
[0102] The final solution was diluted with 13 ml of isododecane to
reach a concentration of 100 g/L.
1-hexene Copolymerisation
[0103] An amount of liquid 1-hexene as indicated in table 2 were
fed in a 250 ml glass vessel reactor at room temperature. The
reactor had been maintained under slight positive nitrogen
atmosphere. Consequently the temperature was increased to the
polymerization temperature indicated in table 2. An over pressure
of 1 bar-g of propylene or 1-butene was fed in the autoclave. The
catalyst solution, (ageing indicated in table 2), was transferred
into the liquid, under a nitrogen flow. The pressure was increased
with propylene until reaching the polymerisation pressure indicated
in table 2. The polymerization was conducted for 60 minutes, then
it was stopped by venting the monomers and the polymer was
precipitated by adding acetone to the polymer solution. The
recovered polymer was dried at 50.degree. C. under vacuum.
Polymerization and polymer data are reported in table 2.
TABLE-US-00002 TABLE 2 Activity Cat 1-hexene Monomer Pol. Temp.
Ageing Kg/g 1-hexene IV Ex (mg. of A-1) g (bar-g) .degree. C. hours
met/h mol % Mw Mw/Mn (THN) dl/g .DELTA.H 2 C-2 (0.38) 67 propylene
(3) 50 1 11 76.5 n.a. n.a. 2.46 n.d. 3 C-2 (0.38) 67 propylene (6)
50 4 32 58.5 n.a. n.a. 2.53 n.d. 4 C-2 (0.31) 40 1-butene (2) 50
450 30 53.1 396371 2.2 3.20 n.d.. 5 C-2 (0.31) 40 1-butene (2) 70
450 43 80.8 285718 1.9 1.33 n.d.. n.a. not available n.d. not
detectable
1-hexene/propylene or 1-butene copolymerisation
[0104] 4 mmol of Al(i-Bu).sub.3 (as a 1M solution in hexane) and
1000 g of 1-hexene were charged at room temperature in a 4-L
jacketed stainless-steel autoclave, previously purified by washing
with an Al(i-Bu).sub.3 solution in hexane and dried at 50.degree.
C. in a stream of nitrogen. The autoclave was then thermostated at
the polymerisation temperature, 70.degree. C., and then the
solution containing the catalyst/cocatalyst solution indicated in
table 3 aged as indicated in table 3 was injected in the autoclave
by means of nitrogen pressure through the stainless-steel vial. The
monomer was fed until a pressure indicated in table 3 and the
polymerisation carried out at constant temperature for 1 hour. The
polymerization solution was discharged into a heated steel tank
containing water at 70.degree. C. The tank heating was switched off
and a flow of nitrogen at 0.5 bar-g was fed. After cooling at room
temperature, the steel tank was opened and the wet polymer
collected and dried at 70.degree. C. under reduced pressure. The
polymerisation conditions and the characterisation data of the
obtained polymers are reported in Table 3.
TABLE-US-00003 TABLE 3 Cat Monomer Activity 1-hexene IV Ex (mg. of
A-1) (bar-g) Kg/g met/h mol % Mw Mw/Mn (THN) dl/g .DELTA.H 6 C-2
(2.58) propylene (20) 83 43 232200 1.9 1.4 n.d. 7 C-2 (1.28)
propylene (19) 117 20.7 229100 2.0 1.51 n.a. 8 C-2 (2.56) 1-butene
(5) 20 41 217200 2.3 1.25 n.d. 9 C-2 (2.6) Propylene (22) 148 46
217433 1.9 1.27 n.d.
[0105] The shore A (ISO 868) of copolymer of examples 6 and 8 has
been measured, the results are reported in table 4. The tensile
modulus of a sample of copolymers obtained in examples 6 and 8 has
been measured according to (ASTM 5026,4092 e 4065) as follows:
Specimens for tensile test are cut from compression moulding
plaques. Specimen sizes are approx. 40 mm long overall, 20 mm
inter-clamp length, 6 mm width and thickness was 1 mm. Specimen is
clamped in the SEIKO DMS 6100 tensile DMTA.
[0106] The applied frequency is 1 Hz.
[0107] Specimens are heated from -80.degree. C. to +140.degree. C.
with 2.degree. C./min as heating rate; specimens are re-clamped at
the low temperature.
[0108] The results are reported in table 4
TABLE-US-00004 TABLE 4 Ex shore A tensile modulus (MPa) 6 19 <10
8 7 <10
Blends
[0109] Samples of copolymers obtained in examples 6, 7 and 9 have
been blended with Moplen.sup.(T)HP500N a propylene homopolymer sold
by Basell. three blends have been obtained by mixing in an extruder
20% of the copolymers of examples 6, 7 and 8 and 80% of Moplen
HP500N. The blends marked as BA (copolymer of example 6); BB
(copolymer of example 7) and BC (copolymer of example) have been
analyzed in order to evaluate the mechanical properties, the
results are reported in table 5
TABLE-US-00005 TABLE 5 Blend BC BA BB HP500N Melt flow rate g/10
min 13.1 13.1 14.3 1.8 Tensile modulus MPa 1275 1130 1060 1450
(DMTA) 23.degree. C. Stress at yield N/MM2 24.8 23.7 21.5 33
Elongation at % 12.3 13 13.5 n.a. yield Stress at break N/MM2 16.6
15.4 12.6 n.a. Elongation at % 70 65 60 n.a. break IZOD at
23.degree. C. J/M 62.9 57.6 55 n.a. IZOD at -20.degree. C. J/M 17
18.5 17 n.a. n.a. not available
[0110] It can be seen that the blend are much more softer than the
homopolymer alone in fact, for example in the blend the tensile
modulus is considerably lowered with respect to the homopolymer
alone.
[0111] A blend of 8% of the copolymer obtained in example 6 and 82%
of Hifax.sup.(T) 7378 heterophasic blend comprising a crystalline
matrix and a rubber phase sold by Basell has been obtained n a
brandbury mixer. The resulting blend (BD) was analysed, the data
are reported in table 6
TABLE-US-00006 TABLE 6 Blend BD Hifax 7378 Flexural modulus MPa
1030 705 IZOD at 23.degree. C. J/M 11.3 11.9 IZOD at -20.degree. C.
J/M 6.6 5.8
* * * * *